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Synthesis of Polylactic Acid

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Synthesis of Polylactic Acid SYNTHESIS OF POLYLACTIC ACID Master’s Thesis Chemical Engineering AAU ESBJERG 30-06-2017 Pranas Vitkevicius SYNTHESIS OF POLYLACTIC ACID Master’s Thesis in Chemical Engineering Period: 09-2016 – 30-06-2017 Supervisors: Erik G. Søgaard and Sergey V. Kucheryavskiy Group: K10K-6-F17 Vitkevicius, Pranas 1 ABSTRACT The goal of this project is to investigate the possibility of using alternative methods, like Ultrasonic Sonochemistry and Microwave Induced Polymerization to synthesize polylactic acid and discuss the possibility of applying mentioned techniques for industrial production. Polylactic acid (PLA) is biodegradable, highly versatile, aliphatic polyester which can be produced from 100 % renewable resources, like corn and beets. PLA proved to be a promising alternative to petroleum-based polymers as its properties are on a par with currently widely used polymers like PET, PVC etc. Current industrial production methods of PLA require high temperatures and high pressures in order to achieve the required final product. Alternative methods, like Sonochemistry and Microwave Induced reaction are growing in popularity and could be considered as faster and more energy- efficient methods to synthesize PLA. Experimental set-up was created according to the information provided in the literature and attempt was made to successfully synthesize PLA with properties comparable to PLA produced by the industrial methods. Analyses of the products were performed using Raman Spectroscopy and then analyzed using Principal Component Analysis (PCA), in order to understand progression of the reaction. None of the produced PLA could be compared to industrial products as resulting polymer showed subpar properties. Analysis with PCA suggested that reaction was happening in the right direction. Experimental set-up should be adjusted further in order to achieve more successful results. However, none of these alternative methods alone seemed to be as a viable pick for industrial application. 2 PREFACE This Master’s Thesis is written by 10th semester student of Master programme in Chemical Engineering at Aalborg University, Esbjerg. The thesis contains overview of the current biopolymer market, overview of possible polylactic acid production paths and attempt to apply alternative techniques, like Ultrasound and Microwaves to achieve high-quality polymer. All plots and charts used for interpretation of spectroscopic data are provided in the report. Full reference list is provided in the end of the report. The author would like to thank Erik G. Søgaard and Sergey V. Kucheryavskiy for supervision and useful advices during the project work. 3 Contents SYNTHESIS OF POLYLACTIC ACID ..................................................................................................... 1 ABSTRACT ....................................................................................................................................... 2 PREFACE ......................................................................................................................................... 3 INTRODUCTION ............................................................................................................................... 7 BIOPLASTICS ................................................................................................................................. 11 Biodegradability ........................................................................................................................ 12 Bioplastics classification ............................................................................................................ 14 POLYLACTIC ACID .......................................................................................................................... 16 Lactic Acid ................................................................................................................................. 16 Polymerization .......................................................................................................................... 17 Direct condensation polymerization ...................................................................................... 18 Melt Polycondesation ............................................................................................................ 20 Ring-Opening Polymerization ................................................................................................ 21 METHODS ..................................................................................................................................... 24 Sonochemistry .......................................................................................................................... 24 Ultrasound ............................................................................................................................ 24 Effects of Ultrasound ............................................................................................................. 25 Microwave Irradiation ............................................................................................................... 30 History of Microwave-Assisted Synthesis ............................................................................... 31 Microwave Radiation ............................................................................................................ 34 Microwave Dielectric Heating ................................................................................................ 36 Dielectric properties .............................................................................................................. 38 Microwave Heating against Thermal Heating ........................................................................ 41 Raman Spectroscopy ................................................................................................................. 43 4 Vibrational Spectroscopy ....................................................................................................... 43 Principles of Raman spectrum ............................................................................................... 45 Preprocessing ............................................................................................................................ 47 Asymmetric least squares for baseline correction ................................................................. 47 Mean Centering .................................................................................................................... 48 Principal Component Analysis ............................................................................................... 48 Synthesis of Polylactic Acid in Literature ................................................................................... 52 EXPERIMENTS AND RESULTS ......................................................................................................... 54 Experimental Set-up .................................................................................................................. 54 Polycondesation .................................................................................................................... 54 Ultrasound initiated polymerization ...................................................................................... 55 Microwave initiated polymerization ...................................................................................... 56 Results ...................................................................................................................................... 57 Polycondensation .................................................................................................................. 57 Prepolymer analysis .............................................................................................................. 58 Ultrasound initiated polymerization .......................................................................................... 60 Microwave induced polymerization .......................................................................................... 71 Discussion ..................................................................................................................................... 78 Ultrasonic Sonochemistry.......................................................................................................... 78 Microwave induced polymerization .......................................................................................... 78 CONCLUSIONS ............................................................................................................................... 80 Ultrasonic Sonochemistry.......................................................................................................... 80 Microwave induced polymerization .......................................................................................... 80 REFERENCES .................................................................................................................................. 81 APPENDIX 1. Synthesis of Poly(Lactic Acid) in Literature ................................................................ 86 5 6 INTRODUCTION Plastics are a wide family of materials derived from organic products, like cellulose, coal, natural gas, salt and crude oil. Plastic materials are considered as extremely resource efficient not only during their production phase, but also during their use phase, meaning that their service life is long and specifically
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